【作者】 陈曦；

【导师】 蹇锡高； 刘程；

【作者基本信息】 大连理工大学 ， 材料与化工（高分子材料）， 2023， 硕士

【摘要】 碳纤增强高性能热塑性树脂基复合材料具有轻质、耐高温、耐腐蚀、高强度、抗冲击、可二次成型、可回收等特点,广泛应用于航空航天、国防工业、汽车制造、海洋船舶等领域。但目前商品化高性能热塑性树脂仍存在耐温等级不足、溶解性差的缺点。本文开发出一种耐温等级更高的可溶性热塑性聚芳醚树脂基体,并以连续碳纤维为增强相,选取两种不同的耐高温热塑性聚芳醚砜酮树脂为基体,制备一系列连续碳纤增强热塑性树脂基复合材料,探究基体结构对复合材料热性能以及力学性能的影响。首先,本文以联苯基双二氮杂萘酮类双酚(4,4′-二苯基联二氮杂萘酮(DBD))、4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(DHPZ)、4,4′-二氟二苯酮(DFK)、4,4′-二氟二苯砜(DFS)为单体,采用高温溶液缩聚反应,DBD与DHPZ两种类双酚单体的摩尔比为8:2,通过调节DFK与DFS的配比,合成了一系列含联苯基双二氮杂萘酮联苯结构共聚芳醚砜酮(PPDESKs)树脂。采用核磁共振氢谱、红外光谱和广角X射线衍射等表征了共聚芳醚砜酮的分子结构,并通过差示扫描量热仪(DSC)和热失重分析仪(TGA)研究了该系列杂环结构共聚芳醚砜酮的热性能,对其进行了溶解性能、流变性能测试,最后,采用溶液浇铸法制膜,并对树脂薄膜进行了拉伸性能测试。测试结果表明,其玻璃化转变温度(T_g)在322-362℃之间,初始分解温度在431-468℃之间,5%热失重温度最高可达514℃。该类杂环结构共聚芳醚砜酮,可溶解于四氯乙烷和NMP强极性非质子性有机溶剂。溶液流变性能测试结果表明其最低粘度为13m Pa·s。聚合物薄膜的拉伸模量在0.76-1.60GPa之间,拉伸强度在69-86MPa之间,断裂伸长率在7.04%-21.32%之间。其次,分别以PPDESKs树脂与砜基双二氮杂萘酮聚芳醚砜酮(PSPSKs)树脂为基体,采用溶液浸渍法制备预浸带,采用模压工艺制备系列连续碳纤维增强杂环结构聚芳醚树脂基复合材料(CF/PPDESKs、CF/PSPSKs)。测试了复合材料的弯曲性能、拉伸性能层间剪切性能及动态热机械性能(DMA),研究结果表明,室温下CF/PSPSKs复合材料弯曲强度、拉伸强度及层间剪切强度分别可达到1502MPa、1671MPa及76MPa,弯曲模量可达166GPa;复合材料高温力学性能测试表明,在330℃下复合材料高温弯曲强度、高温层间剪切强度分别可达547MPa、27MPa。复合材料DMA测试结果表明复合材料储能模量最高可达160GPa,T_g在343-372℃之间。扫描电镜分析表明,复合材料断裂形式由界面脱粘转为基体树脂破坏,进而提高复合材料力学性能。更多还原

【Abstract】 Carbon fiber-reinforced high-performance thermoplastic resin-based composites are lightweight,high temperature resistant,corrosion resistant,high strength,impact resistant,and can be recycled in secondary molding,and are widely used in aerospace,defense industry,automotive manufacturing,and marine shipping.However,the known commercial high performance thermoplastic resins still have the disadvantages of insufficient temperature resistance level and poor solubility.In this paper,a soluble thermoplastic poly(aryl ether)resin matrix with higher temperature resistance grade was developed,and a series of continuous carbon fiber reinforced thermoplastic resin matrix composites were prepared with continuous carbon fiber as the reinforcing phase and two different high temperature resistant thermoplastic poly(aryl ether sulfone)resins were selected as the matrix to investigate the effect of matrix structure on the thermal as well as mechanical properties of the composites.The polymerization reaction of biphenyl-based bis(diazanonaphthalenone)biphenol diphenyl-biphthalazin-dione(DBD),4-(4-hydroxy-phenyl)-2H-phthalazin-1-one(DHPZ),4,4′-difluorodiphenylketone(DFK),and 4,4′-difluorodiphenyl sulfone(DFS)was carried out at high temperature solution,and the molar ratio of DBD to DHPZ biphenol monomers was 8:2.By adjusting the ratio of DFK to DFS,a series of copoly(aryl ether sulfone ketone)containing biphenyl-based bis(diazanonaphthone)biphenyl moieties(PPDESKs)were synthesized.The molecular structure of copolyaryl ether sulfone was characterized by nuclear magnetic resonance hydrogen spectroscopy,infrared spectroscopy and wide-angle X-ray diffraction,and the thermal properties of this series of heterocyclic structure copolyaryl ether sulfone were studied by differential scanning calorimetry(DSC)and thermal weight loss analyzer(TGA),and the dissolution properties and rheological properties were tested,and finally,the film was made by solution casting method and the tensile properties of the resin film were tested.The test results showed that the glass transition temperature(T_g)in the range of 322-362℃,initial decomposition temperature was between 431 and 468℃,and 5%mass loss temperature up to514℃.Which exhibited good solublility in polar aprotic organic solvents,such as tetrachloroethane and NMP.The solution rheological performance test results show a minimum viscosity of 13 m Pa·s at 130℃.The films were prepared by solution casting method,and the tensile properties of the polymer films were tested.And the tensile modulus of the polymer films was ranged from 0.76 GPa to 1.60 GPa,the tensile strength was in the range of 69-86 MPa,and the elongation at break was from 7.04%to 21.32%.Next,a series of carbon fiber reinforced composites(CF/PPDESKs,CF/PSPSKs)were prepared by solution impregnation method and then molding process using PPDESKs resin and sulfone bis(diazanonaphthone)poly(aryl ether sulfone ketone)(PSPSKs)resin as the matrix,respectively.The flexural,tensile and interlaminar shear properties and thermomechanical properties(DMA)of the composites were tested,and the results showed that the flexural,tensile and interlaminar shear strengths of the CF/PSPSKs composites could reach up to 1502MPa,1671 MPa and 76 MPa,respectively,at room temperature,and the flexural modulus was166 GPa.The high temperature flexural strength and high temperature interlaminar shear strength of the composites were reduced by more than 50%at 330℃,and the high temperature flexural modulus was reduced by about 17%.The DMA test results of the composites showed that the energy storage modulus of the composites could reach up to 160 GPa,and the T_g was between 343-372℃.Scanning electron microscopy analysis showed that the fracture form of the composite changed from interfacial debonding to matrix resin damage,improving the mechanical properties of the composite.更多还原